Minimize potential for water readsorption above the 0.5 wt% threshold

DOE-STD-3013-2000

A key conclusion from all the work described above is that plutonium container

environments have inherent self-limiting mechanisms that prevent accumulation

of significant pressures of oxygen and hydrogen over calcined oxides. These

mechanisms are very likely to limit buildup of unacceptable pressures of either

hydrogen or oxygen alone. Known mechanisms limiting oxygen buildup include

recombination with hydrogen and formation of PuO2+x from adsorbed water.

Mechanisms that limit hydrogen buildup include recombination with oxygen to

produce water and probably reduction of PuO2+x and other high valent materials

by hydrogen. It is therefore very likely that the bounding gas assumption made

in this Standard (and in DOE-STD-3013-96) is highly conservative.

4) Minimize potential for water readsorption above the 0.5 wt% threshold

MIS measurements on 33 items from Rocky Flats and Hanford which will be

stabilized according to this Standard, show that pure and impure oxide material

surface areas below 5 m /gram generally result from calcination at 950 C for two

hours. [Haschke/Ricketts 1995; Haschke/Ricketts 1997; Haschke/Martz 1998;

Mason et al. 1999; Manchuron-Mandard/Madic 1996]. This work also shows that

post-calcination water readsorption on oxide particles should not pose a practical

problem with respect to the 0.5 wt% criterion of this Standard (readsorption

onto salt is discussed in the preceding section).

5) Stabilize any other potential gas-producing constituents

This Standard's calcination criterion (2 hrs at 950C) is intended to ensure that in

addition to moisture, all other potential gas-producing impurities in plutonium-

bearing oxide materials are eliminated. The technical literature shows that

nitrates, sulfates and carbonates of plutonium are effectively converted to oxides

by calcination at 950C [Waterbury et al. 1961]. All other nitrates and

carbonates are expected to be decomposed by this procedure. Sulfate is known

to be incorporated into plutonium oxide prepared by peroxide precipitation from

sulfuric acid solutions [Leary et al. 1957]. The report of Moseley and Wing

[Moseley/Wing 1965] shows that 950C calcination is sufficient to destroy this

sulfate constituent. Literature searches indicate that deleterious amounts of

radiolytic gases from residual sulfate and chloride contaminants are unlikely in